CN104137308A - Structured silicon particles - Google Patents

Structured silicon particles Download PDF

Info

Publication number
CN104137308A
CN104137308A CN201380011033.XA CN201380011033A CN104137308A CN 104137308 A CN104137308 A CN 104137308A CN 201380011033 A CN201380011033 A CN 201380011033A CN 104137308 A CN104137308 A CN 104137308A
Authority
CN
China
Prior art keywords
particle
filler
compound particle
compound
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201380011033.XA
Other languages
Chinese (zh)
Other versions
CN104137308B (en
Inventor
威廉·詹姆斯·麦克林
费奥纳·斯科特
克里斯托弗·迈克尔·弗兰德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nexeon Ltd
Original Assignee
Nexeon Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nexeon Ltd filed Critical Nexeon Ltd
Publication of CN104137308A publication Critical patent/CN104137308A/en
Application granted granted Critical
Publication of CN104137308B publication Critical patent/CN104137308B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/44—Alloys based on cadmium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Fuel Cell (AREA)
  • Cell Separators (AREA)

Abstract

A composite particle is provided. The particle comprises a first particle component and a second particle component in which: (a) the first particle component comprises a body portion and a surface portion, the surface portion comprising one or more structural features and one or more voids, whereby the surface portion and body portion define together a structured particle; and (b) the second component comprises a removable filler; characterised in that (i) one or both of the body portion and the surface portion comprise an active material; and (ii) the filler is contained within one or more voids comprised within the surface portion of the first component.; The use of the particle in applications such as electrochemical cells, metal-ion batteries such as secondary battery applications, lithium air batteries, flow cell batteries, fuel cells, solar cells, filters, sensors, electrical and thermal capacitors, micro-fluidic devices, gas or vapour sensors, thermal or dielectric insulating devices, devices for controlling or modifying the transmission, absorption or reflectance of light or other forms of electromagnetic radiation, chromatography or wound dressings is disclosed.

Description

Structured silicon particle
Invention field
The present invention relates to structuring active particle, special but be not exclusively involved in the structured silicon particle for using in following range of application, if electrochemical cell, metal-ion battery group are as secondary battery application, lithium-air battery group, fluid pool battery pack, fuel cell, solar cell, filter, transducer, electric capacity and thermal capacitance, microfluidic devices, gas or vapor sensor, heat or dielectric barrier means, be used for device, chromatography or the wound dressing of transmission, absorption or the reflection of controlling or regulate light or other form electromagnetic radiation.More specifically, the present invention relates to the compound particle that comprises structuring active particle and filler, particularly comprise the structuring activated silica particle of removable filler, relate to its method and their purposes in electrode preparation of preparation.More particularly, the present invention relates to structuring active particle, especially structuring activated silica particle is applied the purposes in especially lithium ion battery group application with them in battery pack.
Background
It should be understood that as used herein term " structuring particle " comprises in its definition: the porous granule substantially as described in WO 2010/128310; Substantially as the porous granule fragment of describing in GB Patent Application No. GB 1115262.6; Substantially that describe as in US2011/0067228, US 2011/0269019, US 2011/0250498 or use in prepared by the technology described in US7402829, JP 2004281317, US 2010/0285358, US 2010/0297502, US2008/0261112 or WO 2011/117436, comprise from particle core extended branch and the particle of the post of branch (hereinafter referred to band post particle) not; Substantially as the fiber of describing in US 8101298, described fiber comprises the hole or the space that distribute in its surface; Substantially thin slice and the band (also have and be distributed in its lip-deep hole or space) described as in US 2010/0190061, and basic as at GB 1115262.6 described in fractal.
All particles disclosed herein can suitably limit by their size and dimension.Not all particle is all proper sphere shape, and will conventionally use main or large-size (or diameter) and less important (or minimum) size or diameter to characterize.For spherical or be spherical particle substantially, main and minor dimension will be normally same or analogous.But as fiber, key dimension will will be pressed fiber thickness definition by fibre length definition and minor dimension conventionally conventionally for the particle extending.Particle also can be according to their aspect ratio definition, and aspect ratio is the big or small ratio of size with the minor dimension of key dimension; For being substantially spherical particle, aspect ratio is by the grade that is 1.The particle extending will conventionally have and be greater than 1, for example, be greater than 2, be greater than 3, be greater than 5 or be greater than 10 aspect ratio.
Can measure by scanning electron microscopy or transmission electron microscopy the size of particle.By measuring length and the thickness in bulk material sample, can obtain average length and thickness.
Composition or powder packets are containing multiple particles with certain size distribution.
The distribution of the particle size in powder can be passed through laser diffraction measurement, it is spherical wherein measured particle being typically assumed to be, and wherein particle diameter is expressed as to spherical equivalent volume diameter, for example, use can derive from the Mastersizer of Malvern Instruments Ltd. tMparticle size analyzer.Spherical equivalent volume diameter is the diameter with the ball of the volume identical with the volume of surveyed particle.If all particles in surveyed powder has identical density, spherical equivalent volume diameter equals spherical equivalent mass diameter, and spherical equivalent mass diameter is to have and the diameter of the ball of the quality identical in quality of surveyed particle.In order to measure, powder is typically dispersed in the medium with the refractive index different from the refractive index of dusty material.The suitable dispersant for powder of the present invention is water.For being of different sizes big or small powder, this particle size analyzer provides spherical equivalent volume diameter distribution curve.
The distribution of sizes of the particle in the powder recording by this way can be expressed as diameter value Dn, and wherein, at least n% of powder volume is formed by the particle with the spherical equivalent volume diameter of measurement that is equal to or less than D.All sizes of quoting herein all refer to D 50value, it is such diameter: wherein at least 50% of powder volume by having the D of being equal to or less than 50the particle of the spherical equivalent diameter of measurement of value forms.
And then, as used herein term " active particle " is appreciated that the particle that expression comprises such material: described material has proper property (for example electricity, electronics, electrochemistry or optical property), makes to comprise that the operation of the product of the particle that comprises this material depends on its proper property.For example, if comprising, particle is inherently electroactive material, this electroactive basis that can form the secondary battery that comprises this particle.Term " electroactive " is appreciated that and represents a kind of such material, in the time that it uses in battery pack application, in point other batteries charging stage and discharge regime process, metal ion as inserting its structure, lithium, sodium, potassium, calcium or magnesium can be neutralized from wherein discharging.Preferably, this material can insert and discharge lithium.If particle comprises the material that represents photovoltaic activity, the particle that comprises this photovoltaic material can for example form in solar cell for.And then, if material is placed on to it therein in the environment of spontaneous corrosion, obtained corrosion current can be drawn and can be by material as the battery to external device (ED) power supply; The device of this type is commonly referred to " fuel cell ", and wherein corrosion material provides fuel.Device as the operation of transducer especially silicon sensor for example depend on the variation of inducing in resistivity or conductivity as the result appearance of the existence of appreciable pollution, and the intrinsic property of such device is resistivity or the conductivity of sensor material.
Therefore as used herein term " structuring active particle " will be understood to represent the structuring particle defined above as this paper, and it comprises the material with intrinsic property, and described intrinsic property forms the operation basis that is formed the device of its part by it.
As used herein " composite material " is appreciated that the material that represents to comprise structuring active particle and select one or more annexing ingredients of the group of free the following composition: adhesive, electric conducting material, filler, auxiliary electroactive material or their mixture.Composite material is conventionally by forming the slurry dried that comprises said components to remove slurries solvent.
As used herein term " electrode material " is appreciated that the composite material that represents that wherein structuring active particle comprises electroactive material.
As used herein term " compound mixture " is appreciated that the composition that expression comprises the slurries of composite material in liquid-carrier.
As used herein term " electrode mixture " is appreciated that the compound mixture that represents that wherein structuring active particle comprises electroactive material.
As used herein term " stable suspension " is appreciated that the dispersion of expression particle in liquid-carrier, and wherein particle does not form or be not inclined to formation aggregation.
The structuring active particle of as described above those can use in multiple application, described application comprises electrochemical cell, metal ion battery pack is as lithium-ion battery group, lithium-air battery group, fluid pool battery pack, other energy accumulating devices are as fuel cell, thermal cell group, photovoltaic devices is as solar cell, filter, transducer, electric capacity and thermal capacitance, microfluidic devices, gases/vapors transducer, heat or dielectric barrier means, for controlling or regulate the transmission of light or other form electromagnetic radiation, the device that absorbs or reflect, chromatography or wound dressing.US 5,914,183 discloses the light-emitting device of the wafer that comprises the quantum wire that is included in its surface formation.
Porous silica particle also can be for the storage of the composition in consumer's nursing, nutrition or medical product or activating agent, controlled delivery or time controlled released.The example of this type porous silica particle is disclosed in US2010/0278931, US 2011/0236493, US 7,332,339, US 2004/0052867, US2007/0255198 and WO 2010/139987.These particles tend in the physiological environment of health, be degraded or absorb.Degradable or absorbable particle are not suitable for being used in multiple application inherently, if electrochemical cell, metal ion battery pack are if lithium-ion battery group, lithium-air battery group, fluid pool battery pack, other energy accumulating devices are if fuel cell, thermal cell group, photovoltaic devices are as solar cell, filter, transducer, electric capacity and thermal capacitance, microfluidic devices, gases/vapors transducer, heat or dielectric barrier means, for controlling or regulate device, chromatography or the wound dressing of transmission, absorption or reflection of light or other form electromagnetic radiation.
The secondary battery that is included in the combination electrode that contains one deck structured silicon particle on current-collector is known and is for example described in: US20100112475, US4002541, US4363708, US7851086, US 2004/0214085, US 2009/0186267, US 2011/0067228, WO 2010/130975, WO 2010/1309766 and WO 2010/128310.
It is believed that and can realize for the continuous needs with the capacity of continuous increase and the secondary battery of cycle life by using highly filled slurries to manufacture combination electrode.In the formation of these battery pack, electrode material used is characterised in that high uniformity and close communication.
Be known that, compared with comprising battery pack natural or not structured silicon particle, comprise that the anodal battery pack that contains structured silicon particle shows good capacity and Life Cycle feature, because structured silicon particle has the tearing tendency of reduction and more can adapt to the stress accumulation in the process in charging and discharging stage of battery pack.And it is highly porous (or can processedly make them be highly porous) and be characterised in that large surface area that structured silicon particle tends to; Although this provides large surface area, on large surface area, can there is the insertion of metal ion and disengage and can improve charge/discharge rates, structure may be fragility inherently.In this case, the preparation of the storage of this structure or amount transport or the electrode material that comprises structured silicon particle may be debatable: although have been found that the stress accumulation that space in structuring electroactive material or passage are minimizing in electrode material is favourable, but they show the physical barriers for the electric charge passage in electrode material, the insertion and the release characteristics that this means structured material are always completely not desirable, and have reduced the internal electrical conductance of electrode material.In addition, if hole is little, electroactive material may not occurred by the abundant moistening of liquid electrolyte, and this has also reduced the wherein efficiency of electric charge transmission; It is almost impossible being soaked into by gel electrolyte.And, sometimes occur, structured silicon particle as the course of processing of the fiber of silicon ribbon post particle, highly porous particle, fiber or porous in, as the result of column bleed, there is the decomposition wholly or in part of particle.This column bleed may be due to, or each particle because with slurries in the collision of other particles and the frictional force that stands or may be the result of the intrinsic Embrittlement of highly porous particle simply.Intrinsic fragility means that processing, storage and the transport of such material are difficult.
Also exist following needs: in the process in active particle is attached to composite material, for example, in the time mixing, by reducing or eliminating caking or the gathering of active particle, improve the dispersion of active particle in composite material in slurries.Gathering may be due to the special size and dimension of active particle, and/or for example, because the state (existence in surface reaction, surface roughness and/or hole) on their surfaces occurs.
Therefore, there are needs for the structuring active particle that can optimize the insertion of lithium and other charge carriers and disengage, particularly in the situation that structuring particle uses in battery pack application.In battery pack and other related application, also the structuring active particle that can optimize the conductivity in material is existed to needs, a part for described material is formed by this structuring active particle.In addition, in battery pack and other purposes, the structuring active particle moistening for the activity that can promote material exists needs, and a part for described material is formed by this structuring active particle.And, for resisting degraded and avoid the structuring active particle of assembling to exist needs in the process of combination electrode manufacture.Method for the preparation of structuring active material is also existed to needs.The present invention is devoted to these needs.
A first aspect of the present invention provides a kind of compound particle that comprises the first particle component and the second particle component, wherein:
(a) described the first particle component comprises body part and surperficial part, and described surface element divides and comprises one or more architectural features and one or more space, thus described surface part and the common limiting structure particle of body part; And
(b) described second component comprises removable filler;
It is characterized in that: (i) described body part and described surface element/mono-or both comprise active material; (ii) described filler is accommodated in the one or more spaces that comprise in the described surperficial part of described the first component; And (iii) described filler has distillation or the decomposition temperature and/or solvable in ionic liquid or electrolyte solution of at least 50 DEG C.
The compound particle of a first aspect of the present invention is not degraded to obvious degree, and be adapted at using in following multiple application, as electrochemical cell, metal ion battery pack is as lithium-ion battery group, lithium-air battery group, fluid pool battery pack, other energy accumulating devices are as fuel cell, thermal cell group, photovoltaic devices is as solar cell, filter, transducer, electric capacity and thermal capacitance, microfluidic devices, gases/vapors transducer, heat or dielectric barrier means, for controlling or regulate the transmission of light or other form electromagnetic radiation, the device that absorbs or reflect, or chromatography or wound dressing purposes.By reducing or eliminating gathering, compound particle can further make active material be evenly dispersed in whole composite material and become easy.For example, can aid dispersion.In addition,, by second component can be removed, active material function in application after manufacture will do not hindered.Compound particle is particularly suitable for using in secondary battery application.Described compound particle is not suitable for, to human body delivered substance, decomposing because they are not inclined in physiological fluid.
The first particle component
The surface part of the first particle component can be defined in particle volume and contain the particle part of the architectural feature of architectural feature or maximum quantity.The existence in the space in surperficial part gives the first particle component intrinsic porousness.
Suitably extend between body part and particle edges (outer surface of surface part) in the architectural feature of surface part and one or more space.The distance that these features extend across defines the thickness of surface part.Architectural feature can comprise post, and it can be branch or branch not.Preferably, architectural feature comprises the not post of branch, more preferably straight, the post of branch not substantially.Each architectural feature can be separated by one or more spaces and adjacent feature.There is the particle of straight post substantially extending from body part and be disclosed in US 2011/0067228, and be typically called as band post particle.Alternatively, architectural feature can be fused to adjacent architectural feature; Or architectural feature be substantially post straight, not branch place along its whole length, or the some place of architectural feature bifurcation from the teeth outwards.The particle of the post that comprises the branch with the point fusing on post surface defines effectively has multiple holes that distribute in its surface or the particle in space; This particle is known as porous granule in WO 2010/128310.Architectural feature and one or more space be suitably distributed in the occupied area of surperficial part at least 20% on, preferably at least 30% and particularly at least 50%.
One or more spaces in surperficial part can be the form of hole or passage aptly.Hole is distributed in the surperficial partly upper of the first particle component aptly, and (for example, via other holes) is communicated with particle edges directly or indirectly.Passage extends to particle edges from body part aptly.Passage can be straight or curl up, but be preferably straight substantially.Hole and passage both provide filler can infiltrate and occupy the path of the void space comprising in the surperficial part of the first particle component.Comprise have solid core and substantially straight post and extend through surface part passage be preferred with post particle as the compound particle of the first particle component.
the Structure mass fraction of the first particle component and structural volume mark
Lip-deep architectural feature in the first particle component can be by the Structure mass fraction of structuring particle (SMF) definition, and it provides by following equation:
SMF=[(is attached to particle core and the quality from the extended structure of particle core)/(gross mass of structuring particle)] x 100%
Therefore,, the in the situation that of activated silica structuring particulate material, should be appreciated that SMF is the quality of silicon structure body quality divided by whole particle.
Can measure SMF by the whole bag of tricks.If structure is to be grown in, to be deposited on or be attached in particle core, can be by measuring the multiple particle core quality in growth or before adhering to and the structuring mass particle in growth or after adhering to, and one is deducted with the quality with above-mentioned equation computation structure body from another, calculate SMF.
If structuring particle is to make to form silicon structure body on the surface of particle core by etch silicon particle, can measure SMF by oxidation technology.This comprises the quality of first measuring some structurings particle, and measure subsequently these some structurings mass particle changes in time in oxidizing process, for example, by heating arrangement particle in oxygen-containing atmosphere, for example, by be heated to 1040 DEG C in air.This structure is first by complete oxidation, and with speed oxidation relatively fast (showing as increasing relatively fast aspect mass penalty speed).In the time observing mass penalty speed and reduce in time and become straight line, think that the oxidation of this structure completes.From now, mass penalty speed is only because the stable oxidation of silicon to particle core causes.The mass penalty of observing is by this mainly because the oxidation of structure causes, and utilizes the density contrast between silicon and silica, can measure the quality of oxidation pre-structure body and therefore can measure PMF.For the powder sample with wide distribution of sizes, can be oxidized extraly compared with the particle core of minor structure particle, and may need to use modifying factor to consider the oxidation of core.Can measure by the sample to comprising without the particle core that structure or structure be removed estimation modifying factor.The method is specially adapted to have the structuring particle of silicon post.
Also can measure SMF by following steps: the quality of measuring a certain amount of structuring particle; For example, by mechanical agitation (as ultrasonic), scraping or chemical erosion, remove structure from particle core; The structure of disengaging is separated and is measured the quality of the quality of this certain amount of particle core and/or the structure of disengaging from particle core.The method is preferred, because it can be for the band post particle of any material.
Percentage (structure density) impact that SMF can cover by structure by the average-size of for example structure, their porositys and particle core.
SMF is preferably greater than or equal to 5%, and more preferably at least 10%, most preferably at least 20%.SMF is preferably not more than 95%, more preferably no more than 80%.Most preferably, SMF is 20-60%, particularly 25-50%.The device that higher SMF value representation high power capacity active structure body forms its part to them has been made larger contribution as the active mass of electrode, and provides and can obtain higher per unit mass total capacity.
But, if SMF value is excessive, the cost of preparing structuring particle may increase, and the Cost And Performance ratio of electrode material is become does not have competitiveness, and the integrality that this structure may become the mechanical/electrical that accumulation too thick and fast and/or post be connected with core may be weakened.
If the density of the material of particle core is obviously different from the density of the material that forms structure, can measure structural volume mark (SVF) to replace SMF, although be to be understood that, SVF is applicable to its center situation substantially the same with structure density (in this case, SVF value will be substantially identical with SMF value), and its center and the visibly different situation of structure density.SVF is provided by following equation:
SVF=[(is from the cumulative volume of the extended structure of described particle core)/(cumulative volume of structuring particle)] x 100%
Can use and the similar method of those methods for measuring SMF, measure SVF.In addition, can use the density ratio of nuclear material and structure material, draw SVF by SMF measured value.The volume of structure and structuring particle is the volume that does not comprise open volume.The blind bore or the hole that are closed in completely in core or structure main body are included in this volume.Therefore,, if structure or core are porous, may need to measure porosity.Can comprise that mercury porosity mensuration and Barret-Joyner-Halenda (BJH) analyze for the case technology of measured hole gap rate.
Porous degree is proportional with the amount of contained void space in the first particle component, and be conventionally reflected in the amount of the void space existing in surperficial part, and be suitably at least 20 volume % of the cumulative volume of surface part, be preferably less than 80 volume %, for example 30 to 70 volume %.Therefore it should be understood that after compound particle forms, coating or filler will occupy some or all of the void space that exists in the surperficial part of dividing in first case subgroup.
As mentioned above, can use volume and the size of MasterSizer system or other similar laser diffractometry measurement device structure and structuring particle.In exemplary method, measure the volume of structuring particle; Structure is departed from from structuring particle as ultrasonic by mechanical treatment; And measure the volume of structure.In the case of the structure or core of porous, measure porosity, and adjust the volume recording.For example, if porosity is 5%, the volume recording is adjusted by 0.95, to provide solid volume.They as mentioned above, also can use the 2D digital imaging system measurement volumes as Morphologi, although typically can not differentiate the particle with the size that is less than 0.5 μ m.
The percentage (structure density) that SVF can be covered by structure by the average-size of for example structure and particle core and the density of particle core and structure material affect.SVF is preferably greater than or equal to 5%, and more preferably at least 10%, most preferably at least 20%.SVF is preferably not more than 95%, more preferably no more than 80%.Most preferably, SVF is 20-60%, particularly 25-50%.Higher SVF value representation high power capacity active structure body has been made larger contribution to the active mass of electrode, and can obtain higher per unit volume total capacity.But, if SVF value is too high, the cost of preparing structuring particle may increase, and the Cost And Performance ratio of electrode material is become does not have competitiveness, and the integrality that structure may become the mechanical/electrical that accumulation too thick and fast and/or structure be connected with core may be weakened.
Particle also can characterize by their specific area, and specific area can be passed through various commercial measurements, comprises BET (Brunauer, Emmett and Teller) and laser diffractometry.
The surface part of the first particle component can comprise have opening to surface, hole or the space of key dimension within the scope of 1nm to 5 μ m.Hole can be 2nm at least, or 5nm at least.Hole can have the size that is not more than 2 μ m.
Specific area, unit mass area or the BET value of the powder being formed by multiple the first particle components preferably reduces by using removable filler, and the first particle component can be more easily mixed in composite material.
Preferably the BET of multiple first particle components with interim filler is not more than 200m 2/ g, more preferably it is not more than 100m 2/ g, or be not more than 80m 2/ g.Most preferably it is not more than 50m 2/ g or be less than 30m 2/ g.Preferably be not more than 90% in the BET value of using after filler with the percentage of the BET value that there is no filler, be preferably not more than 80%, more preferably no more than 60%.The active material of the first particle component suitably comprises electroactive material.Preferably the first particle component comprises the electroactive material that is selected from the group that comprises the following: silicon, tin, germanium, gallium, lead, zinc and aluminium and their electroactive alloy and compound.Electroactive alloy or compound that especially preferred, the first particle component comprises silicon, contain silicon and oxygen, contain silicon and nitrogen compound, the compound, tin, ashbury metal, the compound that contains tin and oxygen that contain silicon and fluorine, contain tin and nitrogen compound and contain tin and the compound of fluorine.The example of the structuring particle that comprises the first particle component includes, but are not limited to: band post particle, porous granule, porous granule fragment and fiber as defined herein.Especially preferred, the first particle component comprises the structuring particle that is selected from the group that comprises the following: siliceous with post particle, porous granule, porous granule fragment and siliceous fiber or their mixture.Especially preferred is the first particle component that comprises silicon ribbon post particle.
The body part that will be appreciated that the first particle component can not have architectural feature, comprises the architectural feature that specific surface part is few or has the structure different from the architectural feature of surface part.Body part suitably limits the core of the architectural feature of stayed surface part.Body part suitably has at 0.1 to 40 μ m, preferably 1 to 35 μ m, more preferably major dimension or the diameter in the scope of 5 to 30 μ m and particularly 5 to 20 μ m.The size of body part can change according to the residing application of this compound particle.In the time that compound particle is comprised in combination electrode, body part suitably has at 0.1 to 40 μ m, preferably 1 to 35 μ m, more preferably major dimension or the diameter in the scope of 5 to 30 μ m and particularly 5 to 20 μ m.
Filler
Removable filler can completely or partially occupy the one or more spaces in surperficial part.Occupying completely of space is appreciated that expression comprises that the hole of filler is full or the meniscus of filler projection above the opening of space.The part in space occupies and is appreciated that and comprises following situation: wherein filler provides the situation of shallow layer on some space walls; Wherein filler only provides the situation of shallow layer on the wall of space; Wherein filler occupies sizable volume in space, but the meniscus of filler is to the situation of extending on the wall of space; Wherein filler has substantially flat meniscus and occupies the situation of sizable volume in space.Use compound particle in battery pack application time, removable filler suitably remain on original position until it in the formation of combination electrode, used or until the formation of battery cell complete.
Removable filler can be included in and be equal to or higher than temperature the distillation dry composite material that comprises compound particle or the material decomposing.Typically, removable filler is at 50 DEG C or higher than 50 DEG C, preferably 70 to 200 DEG C, preferably 80 to 110 DEG C, more preferably in 90 to 100 DEG C of distillations or degraded.Alternatively or additionally, removable filler can be solvable or solvable in the liquid containing the device of composite material at support package at the liquid for washing the composite electrode that comprises compound particle.Preferably, filler therein soluble liquid be selected from the group that comprises the following: electrolyte, electrolyte solvent or ionic liquid.Term " ionic liquid " is appreciated that being illustrated in lower than 100 DEG C is the salt of liquid.Term " electrolyte " is appreciated that and represents the solution of salt in polar solvent.Term " electrolyte solvent " is appreciated that expression can dissolve the polar solvent of organic or inorganic salts.The example of electrolyte solvent comprises that polar solvent is as water, alcohol and organic carbonate.Non-aqueous electrolyte solvent is preferred.The example of operable non-aqueous electrolyte solvent comprises aprotic organic solvent, as 1-METHYLPYRROLIDONE, propylene carbonate, ethylene carbonate, carbonic acid fourth diester, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, 2-dimethoxy-ethane, 2-methyltetrahydrofuran, methyl-sulfoxide, 1, 3-dioxolanes, formamide, dimethyl formamide, acetonitrile, nitromethane, methyl formate, methyl acetate, trimethyl phosphate (phosphoric acid trimester), trimethoxy-methane, sulfolane, methyl sulfolane and 1, 3-dimethyl-2-imidazolinone.
At filler, in electrolyte in soluble situation, it is suitably having the salinity of 0.7M at least, preferably solvable in the electrolyte of the salinity in 0.7 to 2M scope.The example of electrolytic salt includes, but are not limited to LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10c 20, LiPF 6, LiCF 3sO 3, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li and CF 3sO 3li.
Until all remaining on the example of the removable filler of original position, the final preparatory phase of combination electrode comprises having than the higher fusing point of slurries solvent and similarly boiling point or sublimation point, and also insoluble organic or inorganic material therein.In the manufacture process of the composite material that comprises compound particle, removable filler suitably remains on original position.Filler can be removed subsequently together with slurries solvent in the process of drying steps.Alternatively, only can to comprise when compound particle is placed in that it forms in the device of its part be the organic or inorganic material of experience dissolving just to removable filler.Preferably, compound particle uses in the manufacture of battery cell, and filler is dissolved in electrolyte or electrolyte solvent in the time of the formation of battery cell.
Can comprise for the example of the material that covers wholly or in part the first particle component and can be removed after combination electrode forms: o-and p-Cresol, 3-nonyl alcohol, 1 methyl cyclohexanol, p-toluic nitrile, 2-metoxyphenol, 2-phenol-2-propyl alcohol, 2,3-dimethyl anisole, phenol, 2,4-xylenol, 3,4,4-trimethyl amylalcohol, carboxylic acid are as oxalic acid, and butanediol.These coverings or packing material suitably have fusing point between 20 to 30 DEG C and the boiling point of 150 to 200 DEG C.In the drying stage process of manufacturing at electrode, cladding material and slurries solvent removing simultaneously or after it, by distillation, evaporation or degrade and suitably remove.The solid that uses higher is preferred, because this introduces additional porousness in final electrode structure.
Can be for completely or partially covering the first particle component and can comprising wax and surfactant by the example that dissolves the material being removed in the solvent (as electrolyte solvent) being included in device.These coating must be able to dissolve in solvent, and must be stable under the operating condition of device.Compound particle is used in the manufacture of lithium ion battery group, wax or surfactant must be stable in battery pack circulates residing voltage range.
The example of suitable wax comprises that native paraffin is as 12-hydroxy stearic acid, and synthetic wax is as low molecular weight polyethylene, and pertroleum wax is as paraffin, and microwax.
The example of surfactant comprises carboxylate, carboxylic acid amide, sulphonic acid ester, sulfonic acid amides, particularly fatty acid ester and acid amides and alkyl sulfonate esters and acid amides.Surfactant can comprise fluorinated compound.Preferably, surfactant comprises perfluorochemical.
By wax as above, wax mixture or surfactant and other inorganic compounds as Li 2cO 3, LiF, Li 3pO 4, SiO 2, Li 4siO 4, LiAlO 2, Li 2tiO 3, LiNbO 3favourable Deng combination, to improve air stability and polar solvent stability simultaneously.This means that the compound particle that comprises wax filler more easily processes.And, contain the possibility that inorganic component provides use to dissolve the normally used polar solvent of normally used polymer adhesive in the manufacture of composite material.The typically boiling of the temperature in the scope of 120 to 200 DEG C of wax.
In a particularly preferred embodiment of a first aspect of the present invention, interim coating is solvable in the solution of organic carbonate or its mixture, but insoluble or part is solvable in water and/or ethanol.Preferably, solvable in interim filler or coating 0.5 to 2.5M salting liquid in organic carbonate; The example of the soluble suitable salting liquid of coating or filler comprises one or more salt in the group being selected from but be not limited to comprise the following solution in organic carbonate therein: LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10c 20, LiPF 6, LiCF 3sO 3, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3sO 3li and CF 3sO 3li or their mixture.
The compound particle of a first aspect of the present invention can use and well known to a person skilled in the art technology preparation.Such technology comprises that microcapsules technology is as pan coating, centrifugal extrude, spray dry, in-situ polymerization or oligomeric technology, dip coated and sol-gel coating.
Preferably, the first particle component is to comprise the band post particle having from the particle core of the post of its extension.Body part comprises particle core substantially, and the volume that surface part is extended through by the silicon that contains post and one or more spaces limits.Preferably, post and particle core are integrally formed.Suitably, removable filler completely or partially occupies the space around post.When remove filler in the time that combination electrode forms time, thereby finding that the evaporation of filler has moves in the space of the first particle component or near the effect of intensifier electrode material internal connectedness by other components of electrode material.In the time that filler is only solvable in the electrolyte solution in battery pack, has been found that the dissolving of filler causes active material better moistening compared with there is no capped like this material, thereby strengthen the conductivity of the battery pack that comprises structuring active particle.And, have been found that the existence of filler in the space of the first particle component prevented manufacture process center pillar the coming off from core in combination electrode and battery pack.
In with post particle, the diameter of contained post and length will depend on the residing application of band post particle.When with post particle by being comprised in for the combination electrode of lithium ion secondary batteries time, for example, post will typically have the diameter that is greater than 10nm, aptly, the diameter in 30 to 500nm, preferably 40 to 400nm, more preferably 40 to 150nm scope.Column length by aptly at 0.5 to 10 μ m, preferably in the scope of 1 to 5 μ m.Have been found that have 0.5 to 40 μ m, preferably 1 to 25 μ m, more preferably the band post particle of the overall diameter (core adds column length) within the scope of 2 to 15 μ m, particularly 3 to 5 μ m is suitable for secondary battery application.
When the first particle component is when comprising distribution from the teeth outwards and being optionally distributed in the porous granule in the space in particle volume, surface part comprises the particle region (or volume) that coating or filler permeate wherein substantially; In the time that particle is ball, this is by the typically outer volume restriction by ball.Therefore, body part will limit by the particle volume (typically, inside or Assessment of Nuclear Volume) that can not be permeated by filler or coating.In the time that filler or coating permeate whole particle volume, will be appreciated that body part will comprise negligible volume compared with the volume being occupied by surface part.Therefore, will be appreciated that in the time that structuring particle is porous granule, architectural feature comprises the hole, space or the passage that extend to wholly or in part in particle volume, and filler or filler are partially or even wholly distributed in space.
As noted above, interim filler promotes assembly as formed the close communication between other assemblies of its a part of material with post particle or porous granule and they.Interim filler is also by preventing from assembling the uniformity of improving composite material.
The first particle component can (as discussed herein above) in thering is as herein defined the form of the elongate member that is distributed in its lip-deep architectural feature and space, as fiber, silk, line, pipe, thin slice or band.As discussed herein above, the particle of elongation can characterize by less size, larger size and aspect ratio the ratio of less size (the larger size with).Suitably, less important (minimum) of the element of the elongation being provided by its diameter or thickness is of a size of at least 10nm, preferably 30nm at least.The aspect ratio of element of extending is suitably at least 2: 1, preferably at least 3: 1, more preferably at least 5: 1.Preferably, the element of elongation, with the form of fiber, more preferably provides with the form of porous fibre.The element of elongation according to a first aspect of the invention will typically comprise body part and surperficial part.In the time that the first particle component is porous fibre, the internal volume that body part comprises the core that lacks hole, hole or passage.The fibrous external volume of surface element subpackage, its degree of depth partly being extended to by hole or hole defines.
The average and the diameter that will be appreciated that the lip-deep hole, space or the passage that are distributed in the first particle component will use the application of compound particle by depending on wherein.When compound particle involved for the composite material using in the manufacture of secondary battery in time, on the surface of the first particle component, the distribute hole, hole or the passage that arrange preferably have at 1nm to 1500nm, preferably 3.5 to 750nm and the diameter in the scope of 50nm to 500nm particularly.The surface part of the first particle component suitably has the porosity rate in 10 to 70%, preferably 20 to 50% scope, and the quantity of hole, space and passage and diameter are enough to reflect porosity rate.
As discussed herein above, the material that forms body part by it can be identical or different with the material of surface part.When use compound particle or the first particle component in battery pack application time, the surface part of the first particle component suitably comprises electroactive material.Preferably, surface part is formed by the electroactive material that is selected from the group that comprises the following: silicon, gallium, germanium, aluminium, lead, tin, selenium, tellurium, boron and zinc or their electroactive oxide, nitride, hydride, fluoride, alloy, compound and mixture, particularly silicon.Body part can comprise electroactive or non-electroactive material.In the time that body part comprises electroactive material, this can be identical or different with the electroactive material of surface part.The body of the first particle component and surface part can be by etch structures features in the surperficial part of primary, or integrally form by growth structure feature on body part.In first preferred embodiment of a first aspect of the present invention, body part and surface part both comprise electroactive alloy or the compound of silicon or silicon.In the second preferred embodiment, body part comprises the first electroactive material and surface element and divides and comprise the second electroactive material, and described the second electroactive material has the composition different from the first electroactive material of body part.
The surface of the first particle component according to a first aspect of the invention and/or body part can also comprise or alternatively comprise, and as noted herein, self are compound or the mixtures of electroactive electroactive material.Suitable electroactive compound or the example of mixture include, but are not limited to BC, BSi, Si-C, SiGe, SiSn, GeSn, WC, SiO x, SnO x, lithia titanium, TiO 2, binary metal oxide, BN, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, BeSe, BeTe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbSe, PbTe, AgF, AgCl, AgBr, AgI, BeSiN 2, ZnGeP 2, CdSnAs 2, ZnSnSb 2, CuGeP 3, CuSi 2p 3, Si 3n 4, Ge 3n 4, Al 2o 3or Al 2cO.
The first particle component can have 1: 1 to 1: 1000, preferably 1: 1 to 1: 100, the more preferably aspect ratio (ratio of full-size and minimum dimension) in 1: 1 to 1: 50 scope.Therefore the compound particle that will be appreciated that a first aspect of the present invention will also have identical or substantially similar shape and the aspect ratio of the first particle component comprising with it.
The compound particle of a first aspect of the present invention can optionally combine with one or more annexing ingredients, and in the preferred anodal formation of electrode, is formed as the hybrid electro-active material involved as composite layer.The first particle component is by the full diameter or the thickness that also typically have within the scope of 100nm to 100 μ m.
Compound particle according to a first aspect of the invention can easily be prepared, and a second aspect of the present invention provides a kind of method of preparing compound particle according to a first aspect of the invention, said method comprising the steps of: the first particle component is as defined above contacted with removable filler, thereby form filler wherein and fill wholly or in part the compound particle in described space.Comprise that for appropriate technology that the first particle component contact with filler microcapsules technology is as pan coating, air suspension are coated with, centrifugal extrude, spray dry, in-situ polymerization or oligomeric technology, dip coated and sol-gel are coated with.
In the time that removable filler is at room temperature liquid, liquid filling agent can directly mix with the first particle component.Alternatively, in the time that removable filler is at room temperature solid, can provide filler with the form of solution, to inject the space of the first particle component.Preferably, filler or coating are injected in hole, passage or the space of the first particle component.When coating or filler are in the time that room temperature is liquid, capped particle is dried and is stored at the temperature of reduction.When coating or filler are while being at room temperature soluble in solid and the solvent that is being used to form slurries, can be by coating material being heated up to form flowable liquid, or by making filler filler material is dissolved in before contacting with the first particle component to suitable solvent, preferably in organic solvent, form compound particle.To partly depend on the size of architectural feature and the viscosity of filler solution of the first particle component for the condition of guaranteeing filler among architectural feature or effectively inject around, and will easily be determined by those skilled in the art.When pore-size or post are separated special hour, or when filler compared with large infiltration due to the size of particle at need, suitable, the solution of heating filler as far as possible fully injects space partly, surface with the viscosity that fully reduces it to guarantee it.In a preferred embodiment of a second aspect of the present invention, make to be with post particle to mix to form compound particle with removable filler.
In the time that in combination electrode forming process, filler is removable, filler will suitably form by be used to form insoluble material in the solvent of slurries at the temperature that forms combination electrode; Filler suitably have be greater than form electrode temperature, preferred class is similar to or is greater than boiling point or the sublimation point of the boiling point of slurries solvent.The example of the material that can remove in the forming process of combination electrode is oxalic acid.The first particle component is mixed with oxalic acid solution, filter and be dried.Can working strength at 0.001 to 10 % by weight, preferably 0.05 to 5 % by weight, the more preferably careless aqueous acid in the scope of 0.05 to 0.5 % by weight.
In the forming process of device, the example of the filler that can be removed comprises that surfactant is if perfluor-alkyl carboxylic acid or sulphonic acid ester are as perfluor-perfluoroetane sulfonic acid ester.Make the aqueous solution of the first particle component and surfactant as above, and form combination electrode.Can working strength at 0.001 to 10 % by weight, preferably 0.05 to 5 % by weight, the more preferably aqueous solution of the surfactant in the scope of 0.05 to 0.5 % by weight.
The method for filler is contacted with the first particle component that will be appreciated that will depend in part on the character of filler material.
When filler can be in dry composite electrode process or form by being dissolved in the first particle component while being removed in the electrolyte solvent of its a part of battery pack, by forming the slurries of the first particle component in filler solution and mildly stirring these slurries to form the slurries that comprise compound particle, filler is suitably contacted with the first particle component.For thering are on the room temperature of being not less than 15 DEG C, be preferably not less than on room temperature the filler material of the fusing point of 10 DEG C, can be by making solution leniently heat the solution that filler/solvent mixture is easily prepared filler material before contacting with the first particle component.Preferably, in the temperature similar to the temperature of filler, the first particle component is mixed with the solution of filler or filler, to promote filler to the effective injection in the space of the surface part of the first particle component.In the time mixing, if needed, can improve temperature.The liquid slurry that comprises compound particle of gained is suitably dry, to remove or substantially to remove slurries solvent, to provide the compound particle of independent particle, aggregation or dispersion form.The concentration of filler in solution can partly depend on the size of filler molecule; Compared with comprise the coating material of lower-molecular-weight component, suitably provide macromolecule filler with low concentration solution, because this has improved molecule and be injected into the degree of the first particle component.
As discussed herein above, due to the character of the resilience of compound particle, compound particle as referred to herein can use in the manufacture of following multiple device, as electrochemical cell, metal ion battery pack is as lithium-ion battery group, lithium-air battery group, fluid pool battery pack, other energy accumulating devices are as fuel cell, thermal cell group, photovoltaic devices is as solar cell, filter, transducer, electric capacity and thermal capacitance, microfluidic devices, gases/vapors transducer, heat or dielectric barrier means, for controlling or regulate the transmission of light or other form electromagnetic radiation, the device that absorbs or reflect, chromatography or wound dressing, and a third aspect of the present invention provides the purposes in any manufacture of compound particle according to a first aspect of the invention in these devices.
As discussed herein above, compound particle as referred to herein can use in the manufacture of composite material, and a fourth aspect of the present invention provides a kind of method of preparing composite material, said method comprising the steps of: form the compound mixture that comprises compound particle according to a first aspect of the invention, and this compound mixture is coated to base material.Preferably, this composite material is electrode material.Preferably, this compound mixture is electrode mixture.Preferably, this base material is current-collector.The suitably dry current-collector applying.Drying steps can remove interim filler effectively.A fifth aspect of the present invention provides the combination electrode that comprises the current-collector that is coated with one deck electrode material thereon, and wherein said electrode material comprises compound particle according to a first aspect of the invention.
The compound particle of a first aspect of the present invention can use in the manufacture of battery cell, preferably, in the manufacture of secondary cell Battery pack, use, and a sixth aspect of the present invention provides and has comprised positive pole, negative pole, slider and electrolytical battery pack, wherein said positive pole comprises the current-collector that is provided with electrode material on it, and described electrode material comprises compound particle according to a first aspect of the invention.
The battery pack of a sixth aspect of the present invention is easily to manufacture, and a seventh aspect of the present invention provides a kind of method of preparing battery cell, described method comprises: the positive pole, negative pole, slider and the electrolyte that battery case are provided, comprise the electrode material that contains compound particle according to a first aspect of the invention, slider is arranged between positive pole and negative pole, positive pole, negative pole and slider are placed in to battery case, and fill battery case with electrolyte.
The present invention also provides and comprises compound particle according to a first aspect of the invention and the electrode material of one or more components optionally.Include, but are not limited to adhesive and conductive component for the suitable component that is included in electrode material.Preferably, but adhesive is selected from the group that is not limited to comprise the following: polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (NaCMC), polyacrylic acid (PAA), Sodium Polyacrylate (NaPAA), styrene butadiene ribber (SBR), Lithium polyacrylate (LiPAA) and polyimides.In further embodiment, the present invention also provides the method for preparing electrode material, said method comprising the steps of: compound particle is according to a first aspect of the invention provided, and by this compound particle be selected from but be not limited to one or more combination of components of adhesive and conductive carbon.
In a eighth aspect of the present invention, the present invention also provides a kind of composition, it comprises compound particle according to a first aspect of the invention or the stable suspension of composite material according to a forth aspect of the invention in carrier liquid, and in described carrier liquid, filler is not degraded or dissolved.Composition according to an eighth aspect of the invention can be for the compound particle, especially the structuring particle that store or transport defines in a first aspect of the present invention.When composition is according to an eighth aspect of the invention when storing or transport the compound particle that defines in a first aspect of the present invention or structuring particle, filler suitably comprises surfactant, and it contributes to compound particle to remain in suspension for the time period extending.For supporting that the solvent of suspension can be polarity or non-polar solven.And solvent can suitably comprise component that can gelation, it promotes the formation of gel suspended substance, thereby also further increases the stability of composition according to an eighth aspect of the invention.
Now with reference to drawings and Examples, the present invention is described, wherein:
Fig. 1 is compound particle, and it comprises the band post particle (1) as the first particle component, and it has particle core (2) and multiple post from its extension (3).Filler (4) occupies the void space (5) between adjacent post.Although do not draw, being partially filled of space can be included in and on the wall of space, form thin filler coating.
Fig. 2 is compound particle, and it comprises as the porous granule of the first particle component (6) or porous granule fragment (6a), and it has multiple spaces or hole (7,7a).Filler (8,8a) occupies some or all void spaces in particle (6) or particle fragment (6a).The degree of depth (from the surface of particle) that filler is infiltrated is defined as surf zone.
Fig. 3 is compound particle, and it comprises as the fractal of the first particle component (9), and it is porous granule fragment, and fractal comprises body part (10) and multiple nail from its extension (11).Void space (12) will be followed closely (11) and separate, and completely or partially be occupied by filler (13).
Fig. 4 is compound particle, and it comprises the fiber core (14) as the first particle component, and it has the hole (15) forming in its surface, and each hole defines the space in surface structural body.Space is occupied by filler (16) whole or in part.
Fig. 5 is the compound particle comprising as the scaffolding structure body (17) of the first particle component, and described scaffolding structure comprises the structure (18) of the elongation of multiple restriction void spaces (19) boundary.Void space (19) is occupied by filler (20).
Embodiment
The formation of embodiment 1-polyacrylic acid macrogol ester
Embodiment 1a
The ester of polyacrylic acid and polyethylene glycol (MW=4000) is dissolved in deionized water.Final solution contains 0.05 % by weight poly propenoic acid glycol ester.
The formation of embodiment 2-perfluor-perfluoroetane sulfonic acid ester solution.
Perfluor-perfluoroetane sulfonic acid ester is dissolved in aqueous solution, to provide the final solution of the perfluor-perfluoroetane sulfonic acid ester that contains 0.05 % by weight.
Suitable surfactant is sold with FC4330 by 3M, and it contains fluoro aliphatic series polyester.The formation of embodiment 3a-coated particle
The silicon ribbon post particle with the average D50 value in the scope of 3 to 10 μ m is added to as the solution described at embodiment 1 or 2, and stirs 2 to 3 hours.Wet particle is separated by filtering from large quantities of mixtures.Coated particle is dried to afterwards dry in air stream.Characterize the particle of gained by the existence of oxalic acid or perfluor-perfluoroetane sulfonic acid ester.
Embodiment 3b-electrode mixture
By using T25 IKA High Shear 15, in the NMP as carrier liquid, the spherical synthetic graphite of shear-mixed 85 weight portions (d50=27 μ m), the VGCF of 3 weight portions, the comprehensive silicon particle (9 parts as silicon particle and 0.005 part of oxalic acid of explanation in embodiment 1) of 9.2 weight portions and PVdF (9200) the adhesive formation slurries of 2.8 weight portions.The final solids content of slurries is in 30 to 50% scope.The viscosity of slurries is in 1000 to 4500mPa.s scope.The slurries of gained are cast on Copper Foil to the thickness of 60g/cm2.
Embodiment 3c
Use perfluor-perfluoroetane sulfonic acid ester to repeat flow process, to provide the composite material of the silicon particle with the coating of perfluor-perfluoroetane sulfonic acid ester.
The preparation of embodiment 4-battery
Electrode and battery manufacture
Prepare anodal
The compound particle of aequum is added to the bright as noted earlier carbon mix that bead ground in deionized water.Use afterwards T25 IKA High top blender with 1200rpm by the mixture process of gained approximately 3 hours.Add the adhesive of the aequum in solvent or water to this mixture.Finally use ThinkyTM blender by all mixture process approximately 15 minutes, to be given in the composite material described in above embodiment 3a and 3b.
Use technique, cathode mix (3a or 3b) is coated to the thick Copper Foil of 10 μ m (current-collector) upper, to provide the thick coating of 20-35 μ m.Make subsequently the pole drying of gained.In dry run, the composite material that comprises oxalic acid discharges CO 2gas.
Prepare negative pole
The negative material using in test battery is the commercially available lithium MMO electrode material (for example Li1+xNi0.8Co0.15A10.05O2) on stainless steel current-collector.
Electrolyte
The electrolyte using in all batteries is the 1.2M solution that is dissolved in the lithium hexafluoro phosphate in the solvent of the mixture (82%), FEC (15 % by weight) and the VC (3 % by weight) that comprise ethylene carbonate and ethylmethyl carbonate (with the volume ratio of 3: 7).Electrolyte was also used before being placed in battery to the CO dissolving 2saturated.
Battery structure
Be prepared as follows " Swagelok " test cell:
Positive pole and negative pole dish the dried overnight under vacuum of preparation 12mm diameter.
By positive pole dish be placed in by in the 2-electrode battery of accessory assembling.
Be that the Tonen dividing plate that 12.8mm and 16um are thick is placed on anodal dish by two diameters.
Add the electrolyte of 40 μ l to battery.
Negative pole dish is placed on wetting dividing plate to complete battery.
Subsequently the plunger of the 12mm diameter that contains spring is placed on negative pole, and battery gas-tight seal the most at last.Spring pressure remains on the interface of connecting airtight between electrode and electrolyte.
Allow electrolyte to immerse in electrode and continue 30 minutes.
Observation comprises that the structured silicon particle of the coating of perfluor benzene sulfonate has lost their coating material in battery forms.

Claims (41)

1. comprise a compound particle for the first particle component and the second particle component, wherein:
(a) described the first particle component comprises body part and surperficial part, and described surface element divides and comprises one or more architectural features and one or more space, thus described surface part and the common limiting structure particle of body part; And
(b) described second component comprises removable filler;
It is characterized in that: (i) described body part and described surface element/mono-or both comprise active material; (ii) described filler is accommodated in the one or more spaces that comprise in the surperficial part of described the first component; And (iii) described filler has distillation or the decomposition temperature and/or solvable in ionic liquid or electrolyte solution of at least 50 DEG C.
2. compound particle according to claim 1, wherein said filler is solvable in the electrolyte solution with the salinity of 0.7M at least.
3. according to claim 1 or compound particle claimed in claim 2, solvable in the electrolyte solution of the salinity of wherein said filler in the scope with 0.7 to 2M.
4. according to the compound particle described in any one in claims 1 to 3, wherein said filler is solvable in the solution that is selected from the group that comprises the following: 1-METHYLPYRROLIDONE, propylene carbonate, ethylene carbonate, carbonic acid fourth diester, dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, 1, 2-dimethoxy-ethane, 2-methyltetrahydrofuran, methyl-sulfoxide, 1, 3-dioxolanes, formamide, dimethyl formamide, acetonitrile, nitromethane, methyl formate, methyl acetate, trimethyl phosphate, trimethoxy-methane, sulfolane, methyl sulfolane and 1, 3-dimethyl-2-imidazolinone.
5. according to the compound particle described in any one in claim 1 to 4, the temperature of wherein said filler in the scope of 70 to 200 DEG C distils or degraded.
6. compound particle according to claim 5, temperature distillation or the degraded of wherein said filler in the scope of 70 to 110 DEG C.
7. according to the compound particle described in any one in claim 1 to 6, wherein interim filler is selected from the group that comprises the following: o-and p-Cresol, 3-nonyl alcohol, 1 methyl cyclohexanol, p-toluic nitrile, 2-metoxyphenol, 2-phenol-2-propyl alcohol, 2,3-dimethyl anisole, phenol, 2,4-xylenol, 3,4,4-trimethyl amylalcohol, butanediol, oxalic acid, surfactant and be selected from native paraffin or the synthetic wax of the group that comprises the following: 12-hydroxy stearic acid, low molecular weight polyethylene, pertroleum wax are as paraffin and microwax.
8. according to the compound particle described in any one in front claim, wherein said the first particle component is band post particle.
9. compound particle according to claim 8, wherein said surface element divides and comprises one or more posts that are distributed on body part.
10. compound particle according to claim 8 or claim 9, the space of wherein said surface part comprises the passage that extends to described particle edges from described body part.
11. according to the compound particle described in any one in claim 1 to 7, and wherein said the first particle component is porous granule, and described porous granule has from it through the space distributing.
12. compound particles according to claim 11, wherein said porous granule is that minor dimension is fiber, silk, line, pipe, thin slice or the band of at least 10nm.
13. according to the compound particle described in claim 11 or 12, and wherein said space is distributed in the surface of described particle.
14. according to the compound particle described in any one in claim 1 to 7, and wherein said the first particle component is porous granule fragment or fractal.
15. according to the compound particle described in any one in claim 1 to 7, and wherein said the first particle component is scaffolding structure body.
16. according to the compound particle described in any one in front claim, and wherein said particle has the full diameter in the scope of 0.5 to 10 μ m.
17. according to the compound particle described in any one in front claim, and wherein said body part and described surface part are integrally formed, and the active material of the active material that comprises described body part and described surface part is same or similar.
18. according to the compound particle described in any one in claim 1 to 16, and the active material of wherein said body part is different from the active material of described surface part.
19. according to the compound particle described in any one in front claim, and wherein said active material is electroactive material.
20. according to the compound particle described in any one in front claim, and wherein said body part comprises one or more spaces that extend through from it.
21. according to the compound particle described in any one in front claim, and wherein said active material is the electroactive material being selected from the group that comprises the following: silicon, germanium, gallium, lead, aluminium, tin, Se, Te, B, P, binary metal oxide, BC, BSi, Si-C, SiGe, SiSn, GeSn, WC, SiO x, lithia titanium, TiO 2, BN, Bas, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, BeSe, BeTe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbSe, PbTe, AgF, AgCl, AgBr, AgI, BeSiN 2, ZnGeP 2, CdSnAs 2, ZnSnSb 2, CuGeP 3, CuSi 2p 3, Si 3n 4, Ge 3n 4, Al 2o 3, Al 2cO, or their oxide, nitride, hydride, fluoride, mixture or alloy.
22. according to claim 19 to the compound particle described in any one in 21, and wherein electroactive element is selected from silicon, germanium, gallium, tin, lead, aluminium, their oxide, nitride, hydride, fluoride, alloys and mixts.
23. compound particles according to claim 22, wherein said electroactive material is silicon, silicon alloy or electroactive silicon compound.
24. 1 kinds of formation are according to the method for the compound particle described in any one in claim 1 to 23, and described method comprises the first particle component and the step of mixing in the filler of liquid form.
25. methods according to claim 24, wherein said filler provides with solution form.
26. according to the method described in claim 23 or claim 25, and wherein said filler provides with solution form, thereby promotes described filler to the dipping in described space and controllably remove described solvent.
27. methods according to claim 26, wherein remove described solvent by evaporation.
28. 1 kinds of composite materials, described composite material comprises according to compound particle and adhesive described in any one in claim 1 to 23.
29. composite materials according to claim 28, described composite material also comprise from as any one in claim 1 to 23 defined in compound particle different, one or more components of being selected from the following: electroactive carbon, conductive carbon and electroactive component.
30. according to the composite material described in claim 28 or claim 29, and described composite material is electrod composition.
Prepare according to the method for the composite material described in any one in claim 28 to 30 for 31. 1 kinds, said method comprising the steps of: form according to the compound particle described in any one in claim 1 to 23 or according to the composite material described in claim 28 to 30 slurries in suitable solvent, and described slurries are coated on base material and remove described solvent.
32. 1 kinds of electrodes, described electrode comprises according to the compound particle described in any one in claim 1 to 23 or according to the composite material described in claim 28 to 30 and current-collector.
33. electrodes according to claim 29, described electrode is anodal.
Prepare according to the method for the electrode described in claim 32 or 33 for 34. 1 kinds, said method comprising the steps of: form according to the compound particle described in any one in claim 1 to 23 or according to the composite material described in any one in claim 28 to 30 slurries in suitable solvent, described slurries are coated on current-collector and remove described solvent.
35. 1 kinds of electrochemical cells, described electrochemical cell comprises according to the electrode described in claim 29 or 30 and negative pole.
36. 1 kinds of devices, described device comprises electrochemical cell according to claim 35.
37. 1 kinds of compositions, described composition comprise according to the compound particle described in any one in claim 1 to 23 or according to the composite material described in claim 28 to 30 stable suspension in liquid-carrier.
38. according to the composition described in claim 37, and wherein said filler comprises surfactant, so that described compound particle is remained in stable suspension.
39. 1 kinds of storages are according to the compound particle described in any one in claim 1 to 22 or according to the method for the composite material described in claim 28 to 30, and described method is included in the step that forms the stable suspension of described compound particle or composite material in liquid-carrier.
40. according to the method described in claim 37, and described method is also the method for transport.
41. according to the compound particle described in any one in claim 1 to 23 or according to the composite material described in any one in claim 28 to 30 purposes in the manufacture that is selected from one or more devices in the group that comprises the following: electrochemical cell, metal ion battery pack, fuel cell, thermal cell group, photovoltaic devices, solar cell, filter, transducer, electric capacity, thermal capacitance, gases/vapors transducer, heat or dielectric barrier means, for controlling or regulate the transmission of light or other form electromagnetic radiation, the device that absorbs or reflect, chromatogram or wound dressing.
CN201380011033.XA 2012-02-28 2013-02-28 structured silicon particle Expired - Fee Related CN104137308B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB1203447.6 2012-02-28
GB1203447.6A GB2499984B (en) 2012-02-28 2012-02-28 Composite particles comprising a removable filler
PCT/GB2013/050507 WO2013128201A2 (en) 2012-02-28 2013-02-28 Structured silicon particles

Publications (2)

Publication Number Publication Date
CN104137308A true CN104137308A (en) 2014-11-05
CN104137308B CN104137308B (en) 2017-08-25

Family

ID=45991856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380011033.XA Expired - Fee Related CN104137308B (en) 2012-02-28 2013-02-28 structured silicon particle

Country Status (8)

Country Link
US (1) US10103379B2 (en)
EP (1) EP2820703B1 (en)
JP (1) JP6490965B2 (en)
KR (1) KR20140141590A (en)
CN (1) CN104137308B (en)
GB (1) GB2499984B (en)
TW (1) TW201400410A (en)
WO (1) WO2013128201A2 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617271A (en) * 2015-01-29 2015-05-13 中南大学 Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof
CN112142988A (en) * 2019-06-29 2020-12-29 多氟多化工股份有限公司 Polyacrylic acid-polyethylene glycol copolymer and preparation method and application thereof
CN112234189A (en) * 2020-10-13 2021-01-15 深圳大学 Tin telluride-based electrode material, preparation method thereof and lithium ion battery
CN112397705A (en) * 2021-01-18 2021-02-23 湖南雅城新材料有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113363464A (en) * 2021-06-08 2021-09-07 广东工业大学 Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof
CN114725376A (en) * 2022-04-21 2022-07-08 中国工程物理研究院电子工程研究所 Thermal battery cathode material and preparation method and application thereof

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0709165D0 (en) 2007-05-11 2007-06-20 Nexeon Ltd A silicon anode for a rechargeable battery
GB0713898D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries
JP5752696B2 (en) 2009-09-29 2015-07-22 ジョージア テック リサーチ コーポレイション Electrode, lithium ion battery and method for making and using the same
GB2492167C (en) * 2011-06-24 2018-12-05 Nexeon Ltd Structured particles
CN104094454B (en) 2012-01-30 2019-02-01 奈克松有限公司 The composition of SI/C electroactive material
GB2499984B (en) 2012-02-28 2014-08-06 Nexeon Ltd Composite particles comprising a removable filler
GB2502625B (en) 2012-06-06 2015-07-29 Nexeon Ltd Method of forming silicon
US10374221B2 (en) 2012-08-24 2019-08-06 Sila Nanotechnologies, Inc. Scaffolding matrix with internal nanoparticles
GB2507535B (en) 2012-11-02 2015-07-15 Nexeon Ltd Multilayer electrode
KR101704103B1 (en) * 2013-09-17 2017-02-07 주식회사 엘지화학 Porous silicon based anode active material and lithium secondary battery comprising the same
KR101567203B1 (en) 2014-04-09 2015-11-09 (주)오렌지파워 Negative electrode material for rechargeable battery and method of fabricating the same
KR101604352B1 (en) 2014-04-22 2016-03-18 (주)오렌지파워 Negative electrode active material and rechargeable battery having the same
KR101550781B1 (en) 2014-07-23 2015-09-08 (주)오렌지파워 Method of forming silicon based active material for rechargeable battery
DE102014223608A1 (en) * 2014-11-19 2016-05-19 Robert Bosch Gmbh Cathodic electrode of a lithium-based accumulator
GB2533161C (en) 2014-12-12 2019-07-24 Nexeon Ltd Electrodes for metal-ion batteries
KR101614016B1 (en) 2014-12-31 2016-04-20 (주)오렌지파워 Silicon based negative electrode material for rechargeable battery and method of fabricating the same
KR101726037B1 (en) 2015-03-26 2017-04-11 (주)오렌지파워 Silicon based negative electrode material for rechargeable battery and method of fabricating the same
JP7060499B2 (en) * 2015-07-13 2022-04-26 シラ ナノテクノロジーズ インク Stable Lithium Fluoride Cathode for Metals and Metal Ion Batteries
EP3360184A4 (en) 2015-10-05 2019-04-24 Sila Nanotechnologies Inc. Protection of battery electrodes against side reactions
KR102413416B1 (en) 2016-06-14 2022-06-27 넥세온 엘티디 Electrodes for metal-ion cells
CN106058227A (en) * 2016-06-28 2016-10-26 南昌大学 Surface nitriding modification method of silica powder for lithium ion battery
KR101918815B1 (en) 2016-08-23 2018-11-15 넥시온 엘티디. Anode Active Material for Rechargeable Battery and Preparing Method thereof
KR101773719B1 (en) 2016-08-23 2017-09-01 (주)오렌지파워 Silicon based active material for rechargeable battery and method of fabricating the same
JP2018084452A (en) * 2016-11-22 2018-05-31 セイコーエプソン株式会社 Gas cell, magnetic field measurement device, and method for forming gas cell
US20180301698A1 (en) * 2017-04-14 2018-10-18 Rhode Island Council On Postsecondary Education Carboxylic Acids As Surface Modifier for Improved Electrode
GB2563455B (en) 2017-06-16 2019-06-19 Nexeon Ltd Particulate electroactive materials for use in metal-ion batteries
US20220123282A1 (en) * 2018-11-08 2022-04-21 Nexeon Limited Electroactive Materials for Metal-Ion Batteries
JP7318517B2 (en) * 2019-12-19 2023-08-01 トヨタ自動車株式会社 Composite particles for negative electrode active material
CN115336044A (en) * 2020-03-30 2022-11-11 松下知识产权经营株式会社 Coated positive electrode active material and battery using same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212041A (en) * 2006-12-27 2008-07-02 索尼株式会社 Secondary battery electrode, method for manufacturing same, and secondary battery
CN101335342A (en) * 2008-07-30 2008-12-31 郑力 Accumulator electrode with internal particle movable and producing process thereof
US20090137688A1 (en) * 2005-12-23 2009-05-28 Hongli Yang Pharmaceutical product
CN101591478A (en) * 2008-05-26 2009-12-02 李晓冬 Dry surface modification method for electronic grade super-fine silicon micro-powder
CN101656309A (en) * 2006-09-14 2010-02-24 松下电器产业株式会社 Manufacturing negative electrode for lithium ion secondary battery
CN102244251A (en) * 2010-05-14 2011-11-16 三星Sdi株式会社 Negative active material for rechargeable lithium battery and rechargeable lithium battery including same

Family Cites Families (202)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB980513A (en) 1961-11-17 1965-01-13 Licentia Gmbh Improvements relating to the use of silicon in semi-conductor devices
US4002541A (en) 1972-11-03 1977-01-11 Design Systems, Inc. Solar energy absorbing article and method of making same
SU471402A1 (en) 1973-03-02 1975-05-25 Предприятие П/Я Г-4671 Pickling solution
SU544019A1 (en) 1975-07-22 1977-01-25 Одесский Ордена Трудового Красного Знамени Государственный Университет Им.И.И.Мечникова Etcher for semiconductor materials
AU516584B2 (en) 1977-06-01 1981-06-11 Bicc Limited Fabrication of copper
US4192720A (en) 1978-10-16 1980-03-11 Exxon Research & Engineering Co. Electrodeposition process for forming amorphous silicon
DE3020012C2 (en) 1980-05-24 1983-03-03 Daimler-Benz Ag, 7000 Stuttgart Method of exposing the silicon crystals on the surface of a body made of an aluminum alloy with a high silicon content
US4686013A (en) 1986-03-14 1987-08-11 Gates Energy Products, Inc. Electrode for a rechargeable electrochemical cell and method and apparatus for making same
JPS63215041A (en) 1987-03-04 1988-09-07 Toshiba Corp Etching liquid for crystal defect evaluation
JP2997741B2 (en) 1992-07-29 2000-01-11 セイコーインスツルメンツ株式会社 Non-aqueous electrolyte secondary battery and method of manufacturing the same
EP0656668B1 (en) 1993-06-23 1999-03-31 Toray Industries, Inc. Cell electrode, secondary cell using the cell electrode, and method for manufacturing the cell electrode
DE4326944A1 (en) * 1993-08-11 1995-02-16 Varta Batterie Negative electrode for gas-tight alkaline batteries, which has a gas-absorbing layer containing soot
CA2178324C (en) 1993-12-06 2001-02-13 Leigh Trevor Canham Porous semiconductor material
JPH097638A (en) 1995-06-22 1997-01-10 Seiko Instr Inc Nonaqueous electrolytic secondary battery
GB9611437D0 (en) 1995-08-03 1996-08-07 Secr Defence Biomaterial
US6337156B1 (en) 1997-12-23 2002-01-08 Sri International Ion battery using high aspect ratio electrodes
JPH11250896A (en) 1998-02-27 1999-09-17 Sii Micro Parts:Kk Chemical battery
US6132724A (en) 1998-04-29 2000-10-17 City Of Hope National Medical Center Allelic polygene diagnosis of reward deficiency syndrome and treatment
US6376063B1 (en) 1998-06-15 2002-04-23 The Boeing Company Making particulates of controlled dimensions by electroplating
JP2000022162A (en) 1998-07-06 2000-01-21 Advanced Display Inc Manufacturing of liquid crystal display
GB9815819D0 (en) 1998-07-22 1998-09-16 Secr Defence Transferring materials into cells and a microneedle array
US6809229B2 (en) 1999-01-12 2004-10-26 Hyperion Catalysis International, Inc. Method of using carbide and/or oxycarbide containing compositions
DE60128411T2 (en) 2000-02-16 2008-01-17 Nisshinbo Industries, Inc. Multilayer electrode structure and method for its production
JP2001266866A (en) 2000-03-21 2001-09-28 Nippon Steel Corp Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery
US6334939B1 (en) 2000-06-15 2002-01-01 The University Of North Carolina At Chapel Hill Nanostructure-based high energy capacity material
EP1184918B1 (en) 2000-08-28 2009-10-14 Nissan Motor Co., Ltd. Rechargeable lithium ion battery
JP4626105B2 (en) 2000-08-28 2011-02-02 日産自動車株式会社 Lithium ion secondary battery
WO2002021616A1 (en) 2000-09-01 2002-03-14 Sanyo Electric Co., Ltd. Negative electrode for lithium secondary cell and method for producing the same
US6733922B2 (en) * 2001-03-02 2004-05-11 Samsung Sdi Co., Ltd. Carbonaceous material and lithium secondary batteries comprising same
JP4136344B2 (en) 2001-09-05 2008-08-20 アオイ電子株式会社 Lithium secondary battery and manufacturing method thereof
US20030099883A1 (en) 2001-10-10 2003-05-29 Rosibel Ochoa Lithium-ion battery with electrodes including single wall carbon nanotubes
JP3714665B2 (en) 2002-01-25 2005-11-09 Ｎｅｃトーキン栃木株式会社 Method for producing lithium ion secondary battery
JP3897709B2 (en) * 2002-02-07 2007-03-28 日立マクセル株式会社 Electrode material, method for producing the same, negative electrode for non-aqueous secondary battery, and non-aqueous secondary battery
WO2003069027A2 (en) 2002-02-14 2003-08-21 Advanced Silicon Materials Llc Energy efficient method for growing polycrystalline silicon
AU2003221365A1 (en) 2002-03-15 2003-09-29 Canon Kabushiki Kaisha Porous material and process for producing the same
JP3896025B2 (en) 2002-04-10 2007-03-22 三洋電機株式会社 Secondary battery electrode
CN100414743C (en) 2002-05-08 2008-08-27 株式会社杰士汤浅 Nonaqueous electrolyte secondary cell
US20040140222A1 (en) 2002-09-12 2004-07-22 Smedley Stuart I. Method for operating a metal particle electrolyzer
KR100484642B1 (en) 2002-09-23 2005-04-20 삼성에스디아이 주식회사 Positive active material for lithium-sulfur battery and method for preparing the same
GB2395059B (en) 2002-11-05 2005-03-16 Imp College Innovations Ltd Structured silicon anode
JP3664252B2 (en) 2002-11-19 2005-06-22 ソニー株式会社 Negative electrode and battery using the same
JP4046601B2 (en) 2002-12-03 2008-02-13 大阪瓦斯株式会社 Negative electrode material for lithium secondary battery and lithium secondary battery using the same
JP3827642B2 (en) 2003-01-06 2006-09-27 三星エスディアイ株式会社 Negative electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery
CN100452493C (en) * 2003-01-06 2009-01-14 三星Sdi株式会社 Nagative active material for recharge lithium battery, its manufacturing method and recharge lithium battery
US7244513B2 (en) 2003-02-21 2007-07-17 Nano-Proprietary, Inc. Stain-etched silicon powder
JP2004281317A (en) 2003-03-18 2004-10-07 Matsushita Electric Ind Co Ltd Electrode material for nonaqueous electrolyte secondary battery, its manufacturing method and nonaqueous electrolyte secondary battery using it
WO2005011027A2 (en) 2003-07-28 2005-02-03 Showa Denko K.K. High density electrode and battery using the electrode
JP3930002B2 (en) 2003-07-28 2007-06-13 昭和電工株式会社 High density electrode and battery using the electrode
US7479351B2 (en) 2003-10-09 2009-01-20 Samsung Sdi Co., Ltd. Electrode material for a lithium secondary battery, lithium secondary battery, and preparation method for the electrode material for a lithium secondary battery
NO325620B1 (en) * 2003-10-21 2008-06-30 Revolt Technology Ltd Electrode, Method of Preparation thereof, Metal / Air Fuel Cell and Metal Hydride Battery Cell
US8025960B2 (en) 2004-02-02 2011-09-27 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
US20110039690A1 (en) 2004-02-02 2011-02-17 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
US7553371B2 (en) 2004-02-02 2009-06-30 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
CN100338800C (en) 2004-02-17 2007-09-19 比亚迪股份有限公司 Lithium cell plus plate and its preparation method and lithium ion secondary battery
US20050186378A1 (en) 2004-02-23 2005-08-25 Bhatt Sanjiv M. Compositions comprising carbon nanotubes and articles formed therefrom
DE102004016766A1 (en) 2004-04-01 2005-10-20 Degussa Nanoscale silicon particles in negative electrode materials for lithium-ion batteries
CN1263677C (en) 2004-04-22 2006-07-12 华中师范大学 Preparation for composite material with nanometal or metal oxide distributed on surface of carbon nanotube uniformly
JP3799049B2 (en) 2004-05-12 2006-07-19 三井金属鉱業株式会社 Negative electrode for non-aqueous electrolyte secondary battery and method for producing the same
EP1791199B1 (en) 2004-07-20 2012-12-26 Mitsubishi Chemical Corporation Negative electrode material for lithium secondary battery, method for producing same, negative electrode for lithium secondary battery using same and lithium secondary battery
JP4967268B2 (en) * 2004-07-20 2012-07-04 三菱化学株式会社 Negative electrode material for lithium secondary battery, production method thereof, and negative electrode for lithium secondary battery and lithium secondary battery using the same
JP4999292B2 (en) 2004-07-21 2012-08-15 三洋電機株式会社 Non-aqueous electrolyte battery
US20070207318A1 (en) 2004-07-21 2007-09-06 Sungho Jin Catalytically Grown Mano-Bent Nanostructure and Method for Making the Same
US7713849B2 (en) 2004-08-20 2010-05-11 Illuminex Corporation Metallic nanowire arrays and methods for making and using same
JP5256403B2 (en) 2004-09-06 2013-08-07 有限会社ジーイーエム Negative electrode active material particles for lithium secondary battery, negative electrode, and production method thereof
GB2418144A (en) 2004-09-17 2006-03-22 Psimedica Ltd Medical device for delivery of beneficial substance
JP2006134770A (en) 2004-11-08 2006-05-25 Sony Corp Cathode and battery
JP4646612B2 (en) 2004-12-08 2011-03-09 パナソニック株式会社 Negative electrode for nonaqueous electrolyte secondary battery, method for producing the same, and nonaqueous electrolyte secondary battery
JP2006172860A (en) 2004-12-15 2006-06-29 Matsushita Electric Ind Co Ltd Negative electrode for lithium secondary battery and its manufacturing method, and lithium secondary battery
JP4824394B2 (en) 2004-12-16 2011-11-30 パナソニック株式会社 Negative electrode for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery using the same
JPWO2006068066A1 (en) 2004-12-24 2008-06-12 松下電器産業株式会社 Composite electrode active material for non-aqueous electrolyte secondary battery or non-aqueous electrolyte electrochemical capacitor and its production method
US20060147802A1 (en) 2005-01-05 2006-07-06 Kiyotaka Yasuda Anode for nonaqueous secondary battery, process of producing the anode, and nonaqueous secondary battery
WO2006075552A1 (en) 2005-01-11 2006-07-20 Matsushita Electric Industrial Co., Ltd. Material of negative electrode for lithium secondary battery, negative electrode utilizing the material, lithium secondary battery utilizing the negative electrode, and process for producing the material of negative electrode
DE102005011940A1 (en) 2005-03-14 2006-09-21 Degussa Ag Process for the preparation of coated carbon particles and their use in anode materials for lithium-ion batteries
JP4024254B2 (en) 2005-03-23 2007-12-19 三井金属鉱業株式会社 Non-aqueous electrolyte secondary battery
US20060216603A1 (en) 2005-03-26 2006-09-28 Enable Ipc Lithium-ion rechargeable battery based on nanostructures
US7560085B2 (en) 2005-05-09 2009-07-14 Vesta Research, Ltd. Porous silicon particles
JP2006339092A (en) * 2005-06-06 2006-12-14 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte secondary battery and its negative electrode
JP2007019638A (en) 2005-07-05 2007-01-25 Toshiba Corp Key managing device and method thereof
US7851085B2 (en) 2005-07-25 2010-12-14 3M Innovative Properties Company Alloy compositions for lithium ion batteries
US8080334B2 (en) 2005-08-02 2011-12-20 Panasonic Corporation Lithium secondary battery
JP4942319B2 (en) 2005-09-07 2012-05-30 三洋電機株式会社 Lithium secondary battery
KR100745733B1 (en) 2005-09-23 2007-08-02 삼성에스디아이 주식회사 Anode active material, producing method thereof and lithium battery using the same
CN100456533C (en) 2005-11-14 2009-01-28 松下电器产业株式会社 Negative electrode for non-aqueous electrolyte secondary batteries, non-aqueous electrolyte secondary battery having the electrode, and method for producing negative electrode for non-aqueous electrol
JP5162825B2 (en) 2005-12-13 2013-03-13 パナソニック株式会社 Negative electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
FR2895572B1 (en) 2005-12-23 2008-02-15 Commissariat Energie Atomique MATERIAL BASED ON CARBON AND SILICON NANOTUBES FOR USE IN NEGATIVE ELECTRODES FOR LITHIUM ACCUMULATOR
CN101346835B (en) 2005-12-27 2011-06-15 松下电器产业株式会社 Electrode for lithium secondary battery and lithium secondary battery using same
GB0601319D0 (en) 2006-01-23 2006-03-01 Imp Innovations Ltd A method of fabricating pillars composed of silicon-based material
GB0601318D0 (en) 2006-01-23 2006-03-01 Imp Innovations Ltd Method of etching a silicon-based material
CA2535064A1 (en) 2006-02-01 2007-08-01 Hydro Quebec Multi-layer material, production and use thereof as an electrode
TWI368347B (en) * 2006-02-16 2012-07-11 Lg Chemical Ltd Electrode including organic/inorganic composite coating layer and electrochemical device prepared thereby
WO2007094240A1 (en) * 2006-02-17 2007-08-23 Matsushita Electric Industrial Co., Ltd. Electroconductive composite particles, process for producing the electroconductive composite particles, and electrode plate and lithium ion rechargeable battery using the electroconductive composite particles
JP4985949B2 (en) 2006-03-27 2012-07-25 信越化学工業株式会社 Method for producing silicon-silicon oxide-lithium composite, and negative electrode material for non-aqueous electrolyte secondary battery
US7776473B2 (en) 2006-03-27 2010-08-17 Shin-Etsu Chemical Co., Ltd. Silicon-silicon oxide-lithium composite, making method, and non-aqueous electrolyte secondary cell negative electrode material
JP5003047B2 (en) 2006-04-28 2012-08-15 東ソー株式会社 Etching composition and etching method
EA200802296A1 (en) 2006-05-09 2009-04-28 Норск Хюдро Аса METHOD OF PRODUCTION OF SILICON TETRACHLORIDE
JP2007335198A (en) 2006-06-14 2007-12-27 Matsushita Electric Ind Co Ltd Composite active material for nonaqueous secondary battery, and nonaqueous secondary battery using it
JP5200339B2 (en) 2006-06-16 2013-06-05 パナソニック株式会社 Nonaqueous electrolyte secondary battery
JP5398962B2 (en) 2006-06-30 2014-01-29 三洋電機株式会社 Lithium secondary battery and manufacturing method thereof
US7615206B2 (en) 2006-08-11 2009-11-10 Georgia Tech Research Corporation Methods of fabricating nanoscale-to-microscale structures
WO2008044683A1 (en) 2006-10-10 2008-04-17 Panasonic Corporation Negative electrode for nonaqueous electrolyte secondary battery
CN101188281A (en) 2006-11-16 2008-05-28 吴乃立 Cathode active material for lithium ion secondary battery, its making method and lithium ion secondary battery including this cathode active material
WO2008067391A2 (en) 2006-11-28 2008-06-05 Cima Nano Tech Israel Ltd. Process for producing ultra-fine powder of crystalline silicon
JP2008171802A (en) 2006-12-13 2008-07-24 Matsushita Electric Ind Co Ltd Negative electrode for nonaqueous electrolyte secondary battery and its manufacturing method, and nonaqueous electrolyte secondary battery using the same
KR100818263B1 (en) 2006-12-19 2008-03-31 삼성에스디아이 주식회사 Porous anode active material, method of preparing the same, and anode and lithium battery containing the material
JP2008166013A (en) 2006-12-27 2008-07-17 Matsushita Electric Ind Co Ltd Composite active material and electrochemical element using same
JP5143437B2 (en) * 2007-01-30 2013-02-13 日本カーボン株式会社 Method for producing negative electrode active material for lithium ion secondary battery, negative electrode active material, and negative electrode
JP5162934B2 (en) 2007-03-23 2013-03-13 Ｊｓｒ株式会社 Composition for forming upper antireflection film and method for forming resist pattern
KR101400994B1 (en) 2007-04-10 2014-05-29 한국과학기술원 High Capacity Electrode for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same
JP2008269827A (en) 2007-04-17 2008-11-06 Matsushita Electric Ind Co Ltd Electrode material of electrochemical element, its manufacturing method, electrode plate of electrode using it, and electrochemical element
GB0709165D0 (en) 2007-05-11 2007-06-20 Nexeon Ltd A silicon anode for a rechargeable battery
JP4501963B2 (en) * 2007-05-28 2010-07-14 ソニー株式会社 Negative electrode for lithium ion secondary battery and lithium ion secondary battery
JP5218808B2 (en) 2007-06-11 2013-06-26 トヨタ自動車株式会社 Lithium ion battery
GB0713898D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd A method of fabricating structured particles composed of silcon or a silicon-based material and their use in lithium rechargeable batteries
GB0713896D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd Method
GB0713895D0 (en) 2007-07-17 2007-08-29 Nexeon Ltd Production
EP2842582B1 (en) 2007-09-06 2018-06-20 Boston Scientific Limited Medical devices containing silicate and carbon particles
ATE539454T1 (en) 2007-09-14 2012-01-15 Hongfujin Prec Ind Shenzhen LITHIUM BATTERY AND METHOD FOR PRODUCING AN ANODE THEREOF
JP2009099495A (en) 2007-10-19 2009-05-07 Toyota Motor Corp Lithium secondary battery
JP5143700B2 (en) 2007-10-24 2013-02-13 パナソニック株式会社 Electrode for electrochemical element and electrochemical element using the same
KR101522963B1 (en) 2007-11-12 2015-05-26 산요덴키가부시키가이샤 Negative electrode material for rechargeable battery with nonaqueous electrolyte, negative electrode for rechargeable battery with nonaqueous electrolyte, rechargeable battery with nonaqueous electrolyte, and process for producing polycrystalline silicon particles for active material for negative electrode material for rechargeable battery with nonaqueous electrolyte
CN101442124B (en) 2007-11-19 2011-09-07 比亚迪股份有限公司 Method for preparing composite material of lithium ion battery cathode, and cathode and battery
JP2009176719A (en) 2007-12-26 2009-08-06 Sony Corp Electrolyte, secondary battery, and sulfone compound
CN101939862B (en) * 2008-01-08 2014-03-12 赛昂能源有限公司 Porous electrodes and associated methods
US20090186267A1 (en) 2008-01-23 2009-07-23 Tiegs Terry N Porous silicon particulates for lithium batteries
GB2457664A (en) 2008-02-19 2009-08-26 Science Technology Res Partner Electrolyte composition for a dye sensitized solar cell
US20110104480A1 (en) 2008-02-19 2011-05-05 Steven Malekos Targets and processes for fabricating same
JP4998358B2 (en) 2008-04-08 2012-08-15 ソニー株式会社 Negative electrode for lithium ion secondary battery and lithium ion secondary battery
WO2009128800A1 (en) 2008-04-17 2009-10-22 The Board Of Trustees Of The University Of Illinois Silicon nanowire and composite formation and highly pure and uniform length silicon nanowires
US20110111135A1 (en) 2008-07-07 2011-05-12 Yuma Kamiyama Thin film manufacturing method and silicon material that can be used with said method
WO2010006763A1 (en) * 2008-07-15 2010-01-21 Universität Duisburg-Essen Intercalation of silicon and/or tin into porous carbon substrates
FR2935546B1 (en) 2008-09-02 2010-09-17 Arkema France ELECTRODE COMPOSITE MATERIAL, BATTERY ELECTRODE CONSISTING OF SAID MATERIAL AND LITHIUM BATTERY COMPRISING SUCH AN ELECTRODE.
GB0817936D0 (en) 2008-09-30 2008-11-05 Intrinsiq Materials Global Ltd Porous materials
GB2464157B (en) 2008-10-10 2010-09-01 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material
GB2464158B (en) 2008-10-10 2011-04-20 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
US8580432B2 (en) 2008-12-04 2013-11-12 Nanotek Instruments, Inc. Nano graphene reinforced nanocomposite particles for lithium battery electrodes
JP2010135170A (en) 2008-12-04 2010-06-17 Hitachi Vehicle Energy Ltd Lithium secondary battery, secondary battery module, and secondary battery pack
US9263741B2 (en) 2008-12-19 2016-02-16 Nec Energy Devices, Ltd. Negative electrode for nanaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery using the same, and method for manufacturing negative electrode for nonaqueous electrolyte secondary battery
EP2383224B1 (en) 2008-12-26 2016-11-16 Sekisui Chemical Co., Ltd. Process for producing carbon particles for electrode, carbon particles for electrode, and negative-electrode material for lithium-ion secondary battery
KR20110109810A (en) * 2009-01-28 2011-10-06 도요 알루미늄 가부시키가이샤 Carbon-coated aluminum member and method for producing the same
JP2010205609A (en) 2009-03-04 2010-09-16 Nissan Motor Co Ltd Electrode and battery using this
JP2010225494A (en) 2009-03-25 2010-10-07 Shin-Etsu Chemical Co Ltd Anode material for nonaqueous electrolyte secondary battery, its manufacturing method, and lithium ion secondary battery
JP4835881B2 (en) 2009-03-31 2011-12-14 宇部興産株式会社 Lithium ion battery electrode and method for producing the same
EP2427179A4 (en) 2009-05-04 2013-09-11 Psivida Inc Porous silicon drug-eluting particles
US20100285358A1 (en) 2009-05-07 2010-11-11 Amprius, Inc. Electrode Including Nanostructures for Rechargeable Cells
GB2470056B (en) 2009-05-07 2013-09-11 Nexeon Ltd A method of making silicon anode material for rechargeable cells
GB2495951B (en) 2011-10-26 2014-07-16 Nexeon Ltd A composition for a secondary battery cell
GB2470190B (en) 2009-05-11 2011-07-13 Nexeon Ltd A binder for lithium ion rechargeable battery cells
GB0908089D0 (en) * 2009-05-11 2009-06-24 Nexeon Ltd A binder for lithium ion rechargaable battery cells
FR2945378B1 (en) * 2009-05-11 2011-10-14 Commissariat Energie Atomique HIGH TEMPERATURE FUEL CELL CELL WITH INTERNAL HYDROCARBON REFORM.
EP2433475B1 (en) 2009-05-19 2021-04-21 OneD Material, Inc. Nanostructured materials for battery applications
GB0909460D0 (en) 2009-06-02 2009-07-15 Intrinsiq Materials Global Ltd Mesoporus material
TW201106524A (en) 2009-06-29 2011-02-16 Applied Materials Inc Passivation film for solid electrolyte interface of three dimensional copper containing electrode in energy storage device
CN101938013B (en) * 2009-06-30 2014-07-02 比亚迪股份有限公司 Polymer electrolyte and preparation method thereof and polymer lithium secondary battery
IN2012DN02063A (en) 2009-08-28 2015-08-21 Sion Power Corp
CA2772768A1 (en) 2009-09-03 2011-03-10 Molecular Nanosystems, Inc. Methods and systems for making electrodes having at least one functional gradient therein and devices resulting therefrom
GB0917635D0 (en) 2009-10-08 2009-11-25 Intrinsiq Materials Global Ltd Process for the preparation of nano-scale particulate silicon
US7964172B2 (en) 2009-10-13 2011-06-21 Alexander Mukasyan Method of manufacturing high-surface-area silicon
US20110111279A1 (en) 2009-11-09 2011-05-12 Florida State University Research Foundation Inc. Binder-free nanocomposite material and method of manufacture
JP5175826B2 (en) 2009-12-02 2013-04-03 トヨタ自動車株式会社 Active material particles and use thereof
JP5573146B2 (en) 2009-12-21 2014-08-20 パナソニック株式会社 Electrochemical element
JP5617265B2 (en) 2010-02-05 2014-11-05 ソニー株式会社 Negative electrode for lithium ion secondary battery, lithium ion secondary battery, electric tool, electric vehicle and power storage system
CN102754250B (en) 2010-02-19 2015-12-09 松下知识产权经营株式会社 Coin-shaped lithium secondary battery
US9172088B2 (en) 2010-05-24 2015-10-27 Amprius, Inc. Multidimensional electrochemically active structures for battery electrodes
JP5557003B2 (en) 2010-03-19 2014-07-23 株式会社豊田自動織機 Negative electrode material, non-aqueous electrolyte secondary battery, and negative electrode material manufacturing method
ES2350334B1 (en) 2010-03-24 2011-11-11 Alberto Muñoz Herencia PROCESS FOR MEASURING THE QUALITY OF THE SEXUAL STIMULATION OFFERED.
GB201005979D0 (en) 2010-04-09 2010-05-26 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
KR101120053B1 (en) 2010-06-04 2012-03-22 삼화콘덴서공업주식회사 Hybrid super capacitor using composite electrode
JP5676173B2 (en) 2010-08-09 2015-02-25 日本電気株式会社 Method for producing negative electrode for secondary battery
US8526166B2 (en) 2010-08-31 2013-09-03 Samsung Electro-Mechanics Co., Ltd. Lithium ion capacitor
GB201014707D0 (en) 2010-09-03 2010-10-20 Nexeon Ltd Electroactive material
GB201014706D0 (en) 2010-09-03 2010-10-20 Nexeon Ltd Porous electroactive material
JP5535158B2 (en) 2010-09-17 2014-07-02 古河電気工業株式会社 Negative electrode for lithium ion secondary battery, lithium ion secondary battery, and method for producing negative electrode for lithium ion secondary battery
JP5809897B2 (en) 2010-09-17 2015-11-11 古河電気工業株式会社 Porous silicon particles, production method thereof, negative electrode for lithium ion secondary battery, and lithium ion secondary battery
TWI503277B (en) 2010-09-17 2015-10-11 Furukawa Electric Co Ltd Porous silicon particle, porous silicon complex particle and methods for manufacturing thereof
EP2630684A4 (en) 2010-10-22 2015-12-23 Amprius Inc Composite structures containing high capacity porous active materials constrained in shells
DE102010063815A1 (en) 2010-12-21 2012-06-21 Sgl Carbon Se Carbon-silicon multilayer systems
FR2970245B1 (en) 2011-01-07 2013-01-25 Commissariat Energie Atomique SILICON / CARBON COMPOSITE MATERIAL, PROCESS FOR THE SYNTHESIS AND USE OF SUCH A MATERIAL
CN102157731B (en) 2011-03-18 2015-03-04 上海交通大学 Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material
GB2492167C (en) 2011-06-24 2018-12-05 Nexeon Ltd Structured particles
JP2014199714A (en) 2011-08-09 2014-10-23 パナソニック株式会社 Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery
GB2500163B (en) 2011-08-18 2016-02-24 Nexeon Ltd Method
CN103165870B (en) 2011-12-13 2016-03-16 上海杉杉科技有限公司 A kind of silicon based composite material, lithium ion battery and its preparation method and application
CN104094454B (en) 2012-01-30 2019-02-01 奈克松有限公司 The composition of SI/C electroactive material
GB2499984B (en) 2012-02-28 2014-08-06 Nexeon Ltd Composite particles comprising a removable filler
GB201205178D0 (en) 2012-03-23 2012-05-09 Nexeon Ltd Etched silicon structures, method of forming etched silicon structures and uses thereof
KR101368474B1 (en) 2012-03-23 2014-03-03 강원대학교산학협력단 Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
KR20140017646A (en) 2012-03-26 2014-02-11 후루카와 덴키 고교 가부시키가이샤 Negative electrode material for lithium ion secondary batteries, method for producing same, negative electrode for lithium ion secondary batteries using same, and lithium ion secondary battery
GB2502625B (en) 2012-06-06 2015-07-29 Nexeon Ltd Method of forming silicon
KR101634843B1 (en) 2012-07-26 2016-06-29 주식회사 엘지화학 Electrode active material for secondary battery
CN103633295B (en) 2012-08-23 2018-03-02 上海杉杉科技有限公司 A kind of Si-C composite material, lithium ion battery and its preparation method and application
GB2507535B (en) 2012-11-02 2015-07-15 Nexeon Ltd Multilayer electrode
CN103840140B (en) 2012-11-21 2017-12-26 清华大学 porous carbon-silicon composite material and preparation method thereof
KR101494715B1 (en) 2012-11-30 2015-02-23 강원대학교산학협력단 Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same
TWI625885B (en) 2013-01-07 2018-06-01 威廉馬許萊斯大學 Combined electrochemical and chemical etching processes for generation of porous silicon particulates
US20140235884A1 (en) 2013-02-20 2014-08-21 The Governors Of The University Of Alberta Method of preparing silicon nanocrystals
GB2516895C (en) 2013-08-05 2019-05-15 Nexeon Ltd Structured particles
WO2015030531A1 (en) 2013-09-02 2015-03-05 주식회사 엘지화학 Porous silicon based particles, method for preparing same and anode active material comprising same
KR101704103B1 (en) 2013-09-17 2017-02-07 주식회사 엘지화학 Porous silicon based anode active material and lithium secondary battery comprising the same
GB2520946A (en) 2013-12-03 2015-06-10 Nexeon Ltd Electrodes for Metal-Ion Batteries
GB2529411A (en) 2014-08-18 2016-02-24 Nexeon Ltd Electroactive materials for metal-ion batteries
GB2529410A (en) 2014-08-18 2016-02-24 Nexeon Ltd Electroactive materials for metal-ion batteries
GB2533161C (en) 2014-12-12 2019-07-24 Nexeon Ltd Electrodes for metal-ion batteries

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090137688A1 (en) * 2005-12-23 2009-05-28 Hongli Yang Pharmaceutical product
CN101656309A (en) * 2006-09-14 2010-02-24 松下电器产业株式会社 Manufacturing negative electrode for lithium ion secondary battery
CN101212041A (en) * 2006-12-27 2008-07-02 索尼株式会社 Secondary battery electrode, method for manufacturing same, and secondary battery
CN101591478A (en) * 2008-05-26 2009-12-02 李晓冬 Dry surface modification method for electronic grade super-fine silicon micro-powder
CN101335342A (en) * 2008-07-30 2008-12-31 郑力 Accumulator electrode with internal particle movable and producing process thereof
CN102244251A (en) * 2010-05-14 2011-11-16 三星Sdi株式会社 Negative active material for rechargeable lithium battery and rechargeable lithium battery including same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104617271A (en) * 2015-01-29 2015-05-13 中南大学 Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof
CN104617271B (en) * 2015-01-29 2017-01-18 中南大学 Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof
CN112142988A (en) * 2019-06-29 2020-12-29 多氟多化工股份有限公司 Polyacrylic acid-polyethylene glycol copolymer and preparation method and application thereof
CN112142988B (en) * 2019-06-29 2022-12-13 多氟多新材料股份有限公司 Polyacrylic acid-polyethylene glycol copolymer, and preparation method and application thereof
CN112234189A (en) * 2020-10-13 2021-01-15 深圳大学 Tin telluride-based electrode material, preparation method thereof and lithium ion battery
CN112397705A (en) * 2021-01-18 2021-02-23 湖南雅城新材料有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN112397705B (en) * 2021-01-18 2021-05-18 湖南雅城新材料有限公司 Lithium ion battery cathode material and preparation method and application thereof
CN113363464A (en) * 2021-06-08 2021-09-07 广东工业大学 Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof
CN114725376A (en) * 2022-04-21 2022-07-08 中国工程物理研究院电子工程研究所 Thermal battery cathode material and preparation method and application thereof
CN114725376B (en) * 2022-04-21 2023-04-25 中国工程物理研究院电子工程研究所 Thermal battery cathode material and preparation method and application thereof

Also Published As

Publication number Publication date
EP2820703A2 (en) 2015-01-07
EP2820703B1 (en) 2018-12-26
JP2015513180A (en) 2015-04-30
JP6490965B2 (en) 2019-03-27
GB201203447D0 (en) 2012-04-11
US10103379B2 (en) 2018-10-16
GB2499984B (en) 2014-08-06
GB2499984A (en) 2013-09-11
CN104137308B (en) 2017-08-25
TW201400410A (en) 2014-01-01
US20140349183A1 (en) 2014-11-27
WO2013128201A2 (en) 2013-09-06
KR20140141590A (en) 2014-12-10
WO2013128201A3 (en) 2013-11-28

Similar Documents

Publication Publication Date Title
CN104137308A (en) Structured silicon particles
US9368836B2 (en) Additive for lithium ion rechargeable battery cells
US20150140423A1 (en) Composite particle
EP2932542B1 (en) Semi-solid electrodes having high rate capability
CA2808292C (en) Stationary, fluid redox electrode
RU2595710C2 (en) Porous, electrically active material
West et al. Sodium insertion in vanadium oxides
US11557789B2 (en) Solid electrolyte, electrode, power storage device, and method for producing solid electrolytes
JP2016528159A (en) Improved lithium metal oxide rich cathode materials and methods for their preparation
KR101671583B1 (en) High energy density lithium-sulfur battery having interlayer containing active materials
JP5528564B2 (en) Nonaqueous electrolyte secondary battery
JP2014179206A (en) Nonaqueous electrolyte secondary battery
KR20190043163A (en) Solid-liquid electrolyte for use in batteries
US11777143B2 (en) Solid electrolyte, electrode, power storage device, and method for producing solid electrolytes
WO2013047016A1 (en) Negative electrode of non-aqueous electrolyte secondary cell and non-aqueous electrolyte secondary cell
JP5908551B2 (en) Nonaqueous electrolyte battery separator
JP5628385B2 (en) Separator manufacturing method and non-aqueous electrolyte battery
JP2008300099A (en) Lithium secondary cell

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170825

Termination date: 20200228

CF01 Termination of patent right due to non-payment of annual fee